1-chloro-2-methoxybenzene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:25.01; pressure:0.00; stir:

Procedure: General procedure Cwas applied to 1-chloro-2-methoxybenzene 15a(57mg, 0.4mmol). The reaction mixture was stirredat room temperature for 16hoursgiving a conversion of 94% (GC-MS) and 16aand 17ain a 60:40mixture which also contained unreacted starting material 15a(1H NMR spectrum).

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Method B of the above general procedure was followed using 2-chloroanisole (143 mg, 1.01 mmol) and ethyl cyanoacetate (125 mg, 1.11 mmol). The reaction mixture was purified by column chromatography on silica gel (1:3 dichloromethane/hexanes) to give the desired product (191.4 mg, 87%) as a colorless oil: 1H NMR (CDCl3) δ 7.40-7.35 (m, 2H), 7.03-6.99 (m, 1H), 6.93 (d, 8.0 Hz, 1H), 5.03 (s, 1H), 4.30-4.22 (m, 2H), 3.86 (s, 3H), 1.29 (t, 7.2 Hz, 3H). 13C{1H} NMR (CDCl3) δ 165.19, 156.48, 130.73, 129.44, 121.11, 119.11, 115.92, 111.12, 62.97, 55.72, 38.18, 13.97. The reaction mixture was purified by column chromatography on silica gel (1:3 dichloromethane/hexanes)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: According to the general procedure B, 2-Chloroanisole (72 mg, 0.51 mmol) reacted with n-hexylamine (80 μl, 0.60 mmol) using 1 mol % of Pd(OAc)2, 2 mol % of Ph5FcP(t-Bu)2, and sodium tert-butoxide (58 mg, 0.60 mmol) in toluene at 100° C. to give the title compound (102 mg, 97%) as a colorless oil: 1H-NMR (400 MHz, CDCl3): δ 6.93 (t, 1H, J=8.0 Hz, aryl coupling J=0.9 Hz), 6.82 (d, 1H, J=8.0 Hz), 6.66-6.73 (m, 2H), 4.30 (bs, 1H), 3.89 (s, 3H), 3.17 (t, 2H, J=7.2 Hz), 1.71 (m, 2H), 1.51-1.34 (m, 6H), 0.97 (t, 3H, J=6.4 and 6.8 Hz). 13C{1H}-NMR (100 MHz, CDCl3): δ 146.65, 138.39, 121.23, 116.03, 109.71, 109.24, 55.29, 43.63, 31.63, 29.43, 26.88, 22.58, 14.00. GC/MS(EI): m/z 207 (M+). Anal. Calcd for C13H21NO: C, 75.23; H, 10.21; N, 6.76. Found: C,75.41; H, 10.25; N, 6.69. at 100° C.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 6-Bromohexanoyl chloride (2.0 g), 2-chloroanisole (1.17 g) and aluminum chloride (1.12 g) were reacted and treated in the same manner as in Preparation Example 105 to give 0.86 g of 6-bromo-1-(3-chloro-4-methoxyphenyl)-1-hexanone. treated in the same manner as in Preparation Example 105

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Anhydrous aluminum chloride (281 g, 2.104 mol) and 1 L of ethanol-free chloroform were maintained at 0° C. with an ice bath while a solution of acetyl chloride (162 g, 2.28 mol) in 300 mL of chloroform was added over 25 minutes. To this solution was added 2-chloroanisole (250 g, 1.75 mol) in 250 mL of chloroform over 1 hour. The solution was stirred at room temperature for 16 hours and was poured into a mixture of ice and water. The phases were separated and the aqueous phase was extracted with dichloromethane and combined with the original organic phase. The combined organics were dried over anhydrous MgSO4, filtered and concentrated in vacuo to afford a solid which was crystallized from dichloromethane/hexane to give 3-chloro-4-methoxyacetophenone (246 g, 76%) which was used directly in the next step without further purification. was added over 25 minutes The phases were separated the aqueous phase was extracted with dichloromethane The combined organics were dried over anhydrous MgSO4 filtered concentrated in vacuo to afford a solid which was crystallized from dichloromethane/hexane

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir: